This paper discusses a facile route to prepare chain-end functionalized polyolefins containing a terminal functional group (OH, COOH, NH2, etc.), and polyolefin diblock copolymers containing a polyolefin block and a functional polymer block. The chemistry is centered at an in situ chain transfer reaction during metallocene-mediated α-olefin polymerization using two reactive chain transfer (CT) agents, including dialkylborane (R2B-H) and styrenic molecule/H2, to form polyolefin containing a reactive alkylborane and styrenic terminal group, respectively. With the appropriate choice of metallocene catalyst, the polymer formed shows narrow molecular weight distribution (Mw/Mn∼2), and the polymer molecular weight is inversely proportional to the molar ratio of [CT agent]/[α- olefin]. In turn, the terminal borane group is very versatile in interconversion to various polar groups. More importantly, it can be quantitatively transformed to a living radical initiator for chain extension reaction with functional monomers. On the other hand, the terminal styrenic group was then selectively metallated and transformed to a stable polymeric anion for living anionic polymerization. The overall diblock copolymer process resembles a transformation reaction from metallocene-mediated α-olefin polymerization to a living free radical or a living anionic polymerization of functional monomers.
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